We have extended our studies on the enantioselective hydrolyses of racemic acetates by Rhizopus nigricans to yield chiral alcohols of predictable absolute stereochemistries. Our model for predicting the absolute stereochemistry of the alcohols formed is based on the relative sizes of substituents on the carbinol carbon. In order to investigate the influence of more remote substituents on the stereochemical course of these hydrolyses, we have examined the effect of cis- and trans-methyl substituents on C-4 of l-acetoxy-1,2,3,4-tetrahydronaphthalene and 2-acetoxy-1,2,3,4-tetrahydronaphthalene. In the first set of compounds the presence of the C-4 methyl groups does not alter the absolute stereochemistry of the alcohols formed. In the second, the presence of cis- or trans-methyl groups markedly reduces the enantiomeric excesses of the alcohols formed, however, an assignment of the alcohols' configuration based on the hydrolysis results is not in error. Hydrolyses by R. nigricans have also been used to prepare a series of cyclic allylic alcohols, of varying ring size, to test a rule proposed by Nakanishi et al. relating the sign of the c.d. band at 240 nm of a p-bromobenzoate of the alcohol with its absolute stereochemistry. We have found that sign of the c.d. band of cyclooct-2-enyl p-bromobenzoate does not agree with that predicted by the rule.